US8389770B2 - Method for producing diaminodiphenyl alkanes - Google Patents

Method for producing diaminodiphenyl alkanes Download PDF

Info

Publication number
US8389770B2
US8389770B2 US12/867,168 US86716809A US8389770B2 US 8389770 B2 US8389770 B2 US 8389770B2 US 86716809 A US86716809 A US 86716809A US 8389770 B2 US8389770 B2 US 8389770B2
Authority
US
United States
Prior art keywords
process according
weight
aminophenyl
bis
alkane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US12/867,168
Other versions
US20100312014A1 (en
Inventor
Gerda Grund
Manfred Kreczinski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Assigned to EVONIK DEGUSSA GMBH reassignment EVONIK DEGUSSA GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GRUND, GERDA, KRECZINSKI, MANFRED
Publication of US20100312014A1 publication Critical patent/US20100312014A1/en
Application granted granted Critical
Publication of US8389770B2 publication Critical patent/US8389770B2/en
Assigned to EVONIK OPERATIONS GMBH reassignment EVONIK OPERATIONS GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: EVONIK DEGUSSA GMBH
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/78Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines

Definitions

  • the invention relates to a process for preparing diaminodiphenylalkanes (also referred to herein as bis(aminophenyl)alkanes), especially diaminodiphenylmethane.
  • N-alkyl compounds are formed from an aromatic amine (aniline) and aldehyde. These preliminary condensation products then undergo further reaction, in the presence of acidic catalysts, to form aminals. These aminals subsequently undergo rearrangement, under the action of an acidic catalyst, to form diaminodiphenylalkanes.
  • the reaction produces various isomers of the diaminodiphenylalkanes. Mixtures of 2,2′-, 2,4′- and 4,4′-diaminodiphenylalkanes are formed. Also formed, as by-products, are higher condensation products having three to six nuclei, and also N-alkyl compounds.
  • the diaminodiphenylalkanes obtained are processed further to form diisocyanates such as, for example, diisocyanato-dicyclohexylmethane or diisocyanatodiphenylmethane, or other diisocyanates.
  • diisocyanates such as, for example, diisocyanato-dicyclohexylmethane or diisocyanatodiphenylmethane, or other diisocyanates.
  • diaminodiphenylalkanes have frequently been prepared from the condensation of aniline and aldehyde, especially aniline and formaldehyde.
  • reaction according to its particular variant, either first the condensation product of aniline and formaldehyde has been prepared and has then been subjected to rearrangement in the presence of acids such as hydrochloric acid, for example, or else the condensation itself has been carried out in the presence of acids, under rearrangement conditions.
  • a disadvantage of this approach is that, in the case of homogeneous catalysis with mineral acids, salt-containing wastewaters are produced which are formed on neutralization of the acids. Furthermore, the aqueous mineral acids lead to corrosion problems in the production plants. Consequently, in further prior art, processes have been developed which use corresponding heterogeneous catalysts. In these processes, in addition to acidic ion-exchangers, acidic synthetic or natural silicon oxides or aluminium oxides are used as well, such as zeolites or clay minerals.
  • DE-A-12 30 033 describes a process for preparing diaminodiphenylalkanes. It uses silicon-containing clay, a synthetic silicon dioxide-aluminium oxide catalyst or a magnesium oxide-aluminium oxide catalyst.
  • the catalyst it uses is silicon dioxide, silicon dioxide-aluminium oxide or acid-treated aluminium oxide. Preference is given to silica gel or bentonite-like clay which contains silicon dioxide and aluminium oxide and is preferably acid-activated.
  • U.S. Pat. No. 4,071,558 describes a preparation process for preparing diaminodiphenyl-alkanes wherein an acid-activated clay catalyst, a silicon dioxide-aluminium oxide-containing cracking catalyst or a silicon dioxide-magnesium oxide catalyst is used.
  • U.S. Pat. No. 4,039,580 describes a preparation process in which the condensation of aniline and formaldehyde is performed in the absence of a catalyst and then the condensation product is subjected to further reaction in the presence of diatomaceous earth, clays or zeolites to form diaminodiphenylmethane. Similar reactions are also described by U.S. Pat. No. 4,039,581.
  • the catalysts from the group of magnesium oxides or aluminium oxides, clay catalysts or silicon dioxide catalysts have not become established, owing to their high prices, low activities, inconsistent quality and inadequate service lives.
  • EP 0 043 933 A1 describes a process for preparing polyamine mixtures having a high fraction of 4,4′-diaminodiphenylmethane and a low fraction of 2,4′-diaminodiphenylmethane, in which the catalyst used is an ion-exchanger based on a divinylbenzene/styrene copolymer.
  • This ion-exchanger possesses sulphonic acid groups, a specific surface area of 2 to 40 m 2 /g and a pore size of 0.5 to 40 nm.
  • Acidic groups used for the catalyst are sulphonic acid groups. The yields in this process are situated in the range from 60% to 78%. With the sulphonated styrene-divinylbenzene copolymer catalyst it is possible to prepare diaminodiphenylmethanes which possess a high 4,4′-diaminodiphenyl-methane content.
  • the latter isomer is needed in particular for further processing, namely for reaction to form corresponding diisocyanates of the diphenylmethane series, which represent the starting materials in the preparation of polyurethanes or are used as paint base materials.
  • the publication further describes how the fraction of 2,2′- and 2,4′-diisocyanatodiphenylmethane compounds must be extremely low, since for numerous fields of application in the polyisocyanate sector these isomers are unwanted.
  • EP 0 043 933 the resulting diaminodiphenylmethane compounds are immediately subjected to a phosgenation to prepare corresponding diisocyanates.
  • the next stage in the operation of preparing aliphatic isocyanates is the hydrogenation of the aromatic ring of the diaminodiphenylalkanes.
  • the hydrogenation of diaminodiphenylmethane produces, from the 4,4′ isomer, the 4,4′ trans/trans-, cis/cis- and cis/trans-diaminodicyclohexylmethane (PACM).
  • the trans/trans-4,4′-diaminodicyclohexylmethane content has a considerable influence on the crystallization propensity of the diisocyanate.
  • the diisocyanatodicyclohexylmethane may form crystals even at room temperature, which is a hindrance to its further processing to form polyurethanes.
  • Prior to the further processing therefore, costly and inconvenient process steps must be undertaken in order to reduce the 4,4′ isomer content to an acceptable level, so that crystallites are no longer formed. This is usually accomplished by increasing the concentration of the 2,4′ isomer.
  • a further requirement concerning the isomer content in the preparation of diaminodiphenylmethane is that there must be as small as possible a fraction of 2,2′ isomer present, since this isomer causes chain termination in the polymerization reaction during the subsequent step of processing to form polyurethanes.
  • this isomer ratio is obtained by the costly and inconvenient procedure of purifying and distilling the diaminodiphenylmethane in order to be able to provide the isomers in the ratio needed for further processing.
  • the technical problem addressed by the invention therefore, is that of providing a process for preparing diaminodiphenylalkanes that leads directly to the specific isomer ratio required for further processing to the aliphatic diisocyanate and for the corresponding reaction to form polyurethanes, with the fraction of polynuclear compounds formed in the reaction product obtained being extremely low.
  • a further technical problem addressed by the invention is that of developing a process which operates more economically in requiring a shorter reaction time and leading to the desired isomer yields. At the same time the formation of salt-loaded wastewater is also to be avoided.
  • diaminodiphenylalkanes also referred to herein as bis(aminophenyl)alkanes
  • an aromatic amine which may be substituted or unsubstituted
  • a C 1 C 3 aldehyde in the presence of a heterogeneous catalyst
  • the catalyst being a mesoporous acidic ion-exchanger based on a divinylbenzene/styrene copolymer
  • the catalyst having acidic centres, measured in accordance with DIN 54 403, in a concentration of 4 to 6 eq/kg, and the average pore diameter of the catalyst particles, measured in accordance with ASTM D 4222, being 10 to 32 nm, and the polynuclear compound content of the reaction mixture formed being ⁇ 10% by weight.
  • the concentration of the acidic centres of the ion exchanger is 4.4 to 5.7 eq/kg (eq/kg means equivalents per kilogram of ion exchanger) and very preferably 4.7 to 5.6 eq/kg, measured in accordance with DIN 54 403.
  • the acidic centres are preferably acid groups and more preferably sulphonic acid groups.
  • mesoporous ion exchangers are meant those which possess an average pore diameter, measured in accordance with ASTM D 4222, of 2 to 50 nm. In accordance with the invention, however, mesoporous ion exchangers having an average pore diameter of the catalyst particles, measured in accordance with ASTM D 4222, of 10 to 32 nm are used.
  • the pore diameter of the ion exchangers is preferably 15 up to and including 30 nm and very preferably 22 up to and including 30 nm.
  • the properties of these resins can be varied by means of the preparation process.
  • the size of the pores and their distribution is influenced by addition of porogens.
  • Porogens are inert organic substances, solvents or precipitants for example, which during the free-radical suspension polymerization are not included in the polymerization process. After the polymerization they are removed from the polymer again, and are responsible, together with the crosslinker fraction, for the degree of porosity. Porogens serve as solvents for the monomers and as precipitants for the resultant polymers.
  • Porogens used in suspension polymerization include, for example, isopropanol, toluene, heptane, paraffin wax, benzine, amyl alcohol or nitromethane.
  • Use may be made of acidic resins of the divinylbenzene/styrene copolymer that are sold under the following trade names: Duolite®, Amberlyst®, Amberlite®, Dowex®, Lewatit®.
  • Formaldehyde is used preferably as aldehyde.
  • Formaldehyde may be used in the form of aqueous formalin solution or else as formaldehyde in gaseous form. Additionally it is also possible to use compounds which give off formaldehyde under the reaction conditions, such as trioxymethylene or paraformaldehyde, for example. For the reaction it is preferred to use an aqueous formalin solution.
  • Aromatic amines used may be substituted or unsubstituted amines. Preferably the amines, if they are substituted, ought not to possess any substituents in para position.
  • suitable aromatic amines are N-methylaniline, N-ethylaniline, o-toluidine, o-chloroaniline, m-chloroaniline, o-anisidine, 2,3-xylidine, 3,5-xylidine, o-cyclohexylaniline, o-benzylaniline, alpha-naphthylaniline, methylmercaptoaniline or aniline. Particular preference is given to the use of aniline as aromatic amine.
  • composition and isomer ratios are obtained, preferably distributed as follows:
  • diaminodiphenyl-methane with the following isomer composition:
  • the fraction of polynuclear compounds in the isomer mixture of the diaminodiphenylalkane, more particularly of diaminodiphenylmethane, is 10% by weight, preferably ⁇ 10% by weight.
  • Polynuclear compounds for the purposes of the invention are those molecules having more than two aromatic nuclei, more particularly phenyl rings.
  • the N-methyl compound impurities in the isomer mixture of the diaminodiphenylalkane, more particularly diaminodiphenylmethane are ⁇ 1.0% by weight, preferably ⁇ 0.5% by weight and more preferably ⁇ 0.3% by weight.
  • This isomer distribution is particularly suitable for further processing via diaminodicyclohexylmethane to the corresponding diisocyanatodicyclohexylmethane compound.
  • the isomer ratio obtained in the process of the invention also determines the subsequent isomer ratio in the diisocyanate compound.
  • the required isomer ratio is obtained at the diaminodiphenylalkane preparation stage itself, without having to be brought about by means of additional separation processes, which are inconvenient and expensive.
  • additional separation processes which are inconvenient and expensive.
  • purification processes are a disadvantage in view of the fact that the substances involved are very reactive, and so possible side reactions may occur in the course of purification or distillation.
  • a further advantage of the process of the invention is that the fraction of unwanted by-products, especially N-methyl compounds, is very low. On further processing to the diisocyanate, N-methyl compounds lead to unwanted monoisocyanates and hence to a deterioration in the quality of the product.
  • the diaminodiphenylalkanes obtained according to EP 0 043 933 must therefore be brought by means of additional process steps, such as distillation, to the desired isomer ratio of 74% to 85% by weight 4,4′-diaminodiphenylalkane, 3% to 20% by weight 2,4′-diaminodiphenylalkane and ⁇ 1.0% by weight 2,2′-diaminodiphenylalkane.
  • the level of polynuclear compounds, at ⁇ 10% by weight, is favourably low in accordance with the invention.
  • a further advantage of the process of the invention lies in its environmental and economic performance.
  • the catalytic reaction is performed preferably at a reaction temperature in the range from 80 to 140° C., more preferably 80 to 130° C. and very preferably 80 to 120° C.
  • the required reaction time for the catalytic reaction is preferably 30 minutes to 5 hours, more preferably 0.75 hour to 4.5 hours and very preferably 0.75 to 3.0 hours.
  • reaction times are considerably lower in comparison to EP 0 043 933. From the examples of the publication it is apparent that the reaction times there are up to 20 hours and are therefore around twenty times higher than in the case of the process of the present invention.
  • the reaction temperature is similarly high, and this implies an approximately twentyfold higher energy consumption for the implementation of the reaction.
  • the process of the invention therefore possesses the advantage that it can be carried out less expensively and more economically and also, by virtue of the shorter reaction time, affords a greater conversion per unit time.
  • the starting substances used are preferably aromatic amine and aldehyde in a molar ratio of 5:1 to 15:1, preferably 7:1 to 12:1 and very preferably 10:1. It is preferred to use the amine in excess, since this increases the selectivity. Excess amine can be removed by distillation after the conclusion of the reaction.
  • Catalysts used are mesoporous, acidic ion exchangers based on divinylbenzene/styrene copolymers.
  • the catalyst can be used in the dry or moist state.
  • Acidic groups used are preferably sulphonic acid groups.
  • the catalyst is prepared, for example, by copolymerization of styrene with divinylbenzene and sulphonation using sulphuric acid/oleum.
  • the process of the invention can be carried out, in a preferred way, continuously, batchwise or semi-batchwise.
  • the reaction is implemented in a stirred tank, a stirred-tank cascade, a flow tube, one or more fixed-bed reactors, or a column.
  • the catalytic reaction is carried out over a heterogeneous catalyst.
  • the starting substances aromatic amine and aldehyde, are mixed continuously or discontinuously.
  • the catalytic reaction then takes place at temperatures in the range from 80 to 140° C.
  • composition of the reaction product (analysis by gas chromatography following removal of the aniline present in excess) is as follows:
  • composition of the reaction product (analysis by gas chromatography following removal of the aniline present in excess) is as follows:
  • Example 1 shows that the required isomer ratio can be generated without further purification or distillation steps.
  • the reaction times needed for complete formaldehyde conversion were 240 minutes for Example 1, 140 minutes for Example 2 and 60 minutes for Examples 3, 4 and 5.
  • the selectivities (yields) are high and amount to 91.3% by weight in Example 1, 90.5% by weight in Example 2, 90.3% by weight in Example 3, 90% by weight in Example 4 and 90.3% by weight in Example 5.
  • the tables show that the required isomer ratio can be generated without further purification or distillation steps.
  • the selectivity (S) of the reaction is calculated from the ratio between the amount of substance of the desired product (P) formed (in this case the sum of the 2,2′, 2,4′ and 4,4′ isomers of MDA) and the amount of substance of the key component (K) reacted (in this case formaldehyde), taking into account the stoichiometric numbers (v).
  • S selectivity

Abstract

The invention relates to a method for producing diaminodiphenyl alkanes, wherein an aromatic amine, which can be substituted or unsubstituted, is reacted with a C1-C3 aldehyde in the presence of a heterogeneous catalyst, said catalyst being a mesoporous acidic ion exchanger based on a divinylbenzene/styrene copolymer and the catalyst having acid centers in a concentration of 4 to 6 eq/kg as measured according to DIN 54 403 and the average pore diameter of the catalyst particles being 10 to 32 nm as measured according to ASTM D 4222 10, and the content of polynuclear compounds in the reaction mixture being ≰10% by weight.

Description

The invention relates to a process for preparing diaminodiphenylalkanes (also referred to herein as bis(aminophenyl)alkanes), especially diaminodiphenylmethane.
The preparation of diaminodiphenylalkanes by condensation of an aromatic amine such as aniline and aldehyde over acidic catalysts is known.
In the reaction, first of all, N-alkyl compounds are formed from an aromatic amine (aniline) and aldehyde. These preliminary condensation products then undergo further reaction, in the presence of acidic catalysts, to form aminals. These aminals subsequently undergo rearrangement, under the action of an acidic catalyst, to form diaminodiphenylalkanes.
The reaction produces various isomers of the diaminodiphenylalkanes. Mixtures of 2,2′-, 2,4′- and 4,4′-diaminodiphenylalkanes are formed. Also formed, as by-products, are higher condensation products having three to six nuclei, and also N-alkyl compounds.
According to the known state of the art, the diaminodiphenylalkanes obtained are processed further to form diisocyanates such as, for example, diisocyanato-dicyclohexylmethane or diisocyanatodiphenylmethane, or other diisocyanates. These compounds are important paint base materials and base products for, for example, the preparation of polyurethanes.
In the prior art, diaminodiphenylalkanes have frequently been prepared from the condensation of aniline and aldehyde, especially aniline and formaldehyde. In that reaction, according to its particular variant, either first the condensation product of aniline and formaldehyde has been prepared and has then been subjected to rearrangement in the presence of acids such as hydrochloric acid, for example, or else the condensation itself has been carried out in the presence of acids, under rearrangement conditions.
A disadvantage of this approach is that, in the case of homogeneous catalysis with mineral acids, salt-containing wastewaters are produced which are formed on neutralization of the acids. Furthermore, the aqueous mineral acids lead to corrosion problems in the production plants. Consequently, in further prior art, processes have been developed which use corresponding heterogeneous catalysts. In these processes, in addition to acidic ion-exchangers, acidic synthetic or natural silicon oxides or aluminium oxides are used as well, such as zeolites or clay minerals.
In U.S. Pat. No. 4,294,981, in a process of this kind, the condensation is carried out in the presence of a strong aqueous acid, the acid being subsequently removed by solvent extraction. The rearrangement is carried out in turn in the presence of a strong acid, which is used in a relatively small amount. Diatomaceous earth, clays or zeolites can be used as catalysts in this reaction stage.
DE-A-12 30 033 describes a process for preparing diaminodiphenylalkanes. It uses silicon-containing clay, a synthetic silicon dioxide-aluminium oxide catalyst or a magnesium oxide-aluminium oxide catalyst.
Another reaction process for preparing diaminodiphenylalkanes is described in DE-A-14 93 431. The catalyst it uses is silicon dioxide, silicon dioxide-aluminium oxide or acid-treated aluminium oxide. Preference is given to silica gel or bentonite-like clay which contains silicon dioxide and aluminium oxide and is preferably acid-activated.
U.S. Pat. No. 4,071,558 describes a preparation process for preparing diaminodiphenyl-alkanes wherein an acid-activated clay catalyst, a silicon dioxide-aluminium oxide-containing cracking catalyst or a silicon dioxide-magnesium oxide catalyst is used.
U.S. Pat. No. 4,039,580 describes a preparation process in which the condensation of aniline and formaldehyde is performed in the absence of a catalyst and then the condensation product is subjected to further reaction in the presence of diatomaceous earth, clays or zeolites to form diaminodiphenylmethane. Similar reactions are also described by U.S. Pat. No. 4,039,581.
The catalysts from the group of magnesium oxides or aluminium oxides, clay catalysts or silicon dioxide catalysts have not become established, owing to their high prices, low activities, inconsistent quality and inadequate service lives.
In the more recent prior art, therefore, the proposal is made to prepare diamino-diphenylalkanes using as the catalyst an ion-exchanger which possesses acidic groups. EP 0 043 933 A1, for instance, describes a process for preparing polyamine mixtures having a high fraction of 4,4′-diaminodiphenylmethane and a low fraction of 2,4′-diaminodiphenylmethane, in which the catalyst used is an ion-exchanger based on a divinylbenzene/styrene copolymer. This ion-exchanger possesses sulphonic acid groups, a specific surface area of 2 to 40 m2/g and a pore size of 0.5 to 40 nm. Acidic groups used for the catalyst are sulphonic acid groups. The yields in this process are situated in the range from 60% to 78%. With the sulphonated styrene-divinylbenzene copolymer catalyst it is possible to prepare diaminodiphenylmethanes which possess a high 4,4′-diaminodiphenyl-methane content. The latter isomer is needed in particular for further processing, namely for reaction to form corresponding diisocyanates of the diphenylmethane series, which represent the starting materials in the preparation of polyurethanes or are used as paint base materials. The publication further describes how the fraction of 2,2′- and 2,4′-diisocyanatodiphenylmethane compounds must be extremely low, since for numerous fields of application in the polyisocyanate sector these isomers are unwanted. According to the prior art EP 0 043 933, the resulting diaminodiphenylmethane compounds are immediately subjected to a phosgenation to prepare corresponding diisocyanates.
The process described in EP 0 043 933 for preparing diaminodiphenylalkanes has the disadvantage that it possesses low yields and that, in spite of a high reaction temperature, very long reaction times are needed in order to achieve an industrially acceptable yield. A further disadvantage is that the prior-art process produces only a small fraction of 2,4′ isomer.
As well as aromatic isocyanates, the corresponding aliphatic isocyanates are particularly important in certain speciality sectors.
The next stage in the operation of preparing aliphatic isocyanates is the hydrogenation of the aromatic ring of the diaminodiphenylalkanes.
The hydrogenation of diaminodiphenylmethane produces, from the 4,4′ isomer, the 4,4′ trans/trans-, cis/cis- and cis/trans-diaminodicyclohexylmethane (PACM). The trans/trans-4,4′-diaminodicyclohexylmethane content has a considerable influence on the crystallization propensity of the diisocyanate. If the trans/trans 4,4′ fraction of the diisocyanate product prepared from PACM by phosgenation or other processes is too high, the diisocyanatodicyclohexylmethane may form crystals even at room temperature, which is a hindrance to its further processing to form polyurethanes. Prior to the further processing, therefore, costly and inconvenient process steps must be undertaken in order to reduce the 4,4′ isomer content to an acceptable level, so that crystallites are no longer formed. This is usually accomplished by increasing the concentration of the 2,4′ isomer.
A further requirement concerning the isomer content in the preparation of diaminodiphenylmethane is that there must be as small as possible a fraction of 2,2′ isomer present, since this isomer causes chain termination in the polymerization reaction during the subsequent step of processing to form polyurethanes.
An additional requirement concerning the preparation of diaminodiphenylmethane is that the fraction of polynuclear compounds formed in the reaction product obtained is extremely low.
In order to avoid this additional cost and complexity, it is important, for this reaction route, to obtain a defined isomer ratio during the preparation of the diaminodiphenylmethane itself.
According to the state of the art to date, this isomer ratio is obtained by the costly and inconvenient procedure of purifying and distilling the diaminodiphenylmethane in order to be able to provide the isomers in the ratio needed for further processing.
The technical problem addressed by the invention, therefore, is that of providing a process for preparing diaminodiphenylalkanes that leads directly to the specific isomer ratio required for further processing to the aliphatic diisocyanate and for the corresponding reaction to form polyurethanes, with the fraction of polynuclear compounds formed in the reaction product obtained being extremely low. A further technical problem addressed by the invention is that of developing a process which operates more economically in requiring a shorter reaction time and leading to the desired isomer yields. At the same time the formation of salt-loaded wastewater is also to be avoided.
This technical problem is solved by a process for preparing diaminodiphenylalkanes (also referred to herein as bis(aminophenyl)alkanes), where an aromatic amine, which may be substituted or unsubstituted, is reacted with a C1 C3 aldehyde in the presence of a heterogeneous catalyst, the catalyst being a mesoporous acidic ion-exchanger based on a divinylbenzene/styrene copolymer, and the catalyst having acidic centres, measured in accordance with DIN 54 403, in a concentration of 4 to 6 eq/kg, and the average pore diameter of the catalyst particles, measured in accordance with ASTM D 4222, being 10 to 32 nm, and the polynuclear compound content of the reaction mixture formed being ≦10% by weight.
In one preferred embodiment the concentration of the acidic centres of the ion exchanger is 4.4 to 5.7 eq/kg (eq/kg means equivalents per kilogram of ion exchanger) and very preferably 4.7 to 5.6 eq/kg, measured in accordance with DIN 54 403.
The acidic centres are preferably acid groups and more preferably sulphonic acid groups.
By mesoporous ion exchangers are meant those which possess an average pore diameter, measured in accordance with ASTM D 4222, of 2 to 50 nm. In accordance with the invention, however, mesoporous ion exchangers having an average pore diameter of the catalyst particles, measured in accordance with ASTM D 4222, of 10 to 32 nm are used.
The pore diameter of the ion exchangers, measured in accordance with ASTM D 4222, is preferably 15 up to and including 30 nm and very preferably 22 up to and including 30 nm.
The properties of these resins, more particularly specific surface area, porosity, stability and exchange capacity, can be varied by means of the preparation process. Thus, for example, the size of the pores and their distribution is influenced by addition of porogens. Porogens are inert organic substances, solvents or precipitants for example, which during the free-radical suspension polymerization are not included in the polymerization process. After the polymerization they are removed from the polymer again, and are responsible, together with the crosslinker fraction, for the degree of porosity. Porogens serve as solvents for the monomers and as precipitants for the resultant polymers. Porogens used in suspension polymerization include, for example, isopropanol, toluene, heptane, paraffin wax, benzine, amyl alcohol or nitromethane.
Use may be made of acidic resins of the divinylbenzene/styrene copolymer that are sold under the following trade names: Duolite®, Amberlyst®, Amberlite®, Dowex®, Lewatit®.
Formaldehyde is used preferably as aldehyde. Formaldehyde may be used in the form of aqueous formalin solution or else as formaldehyde in gaseous form. Additionally it is also possible to use compounds which give off formaldehyde under the reaction conditions, such as trioxymethylene or paraformaldehyde, for example. For the reaction it is preferred to use an aqueous formalin solution.
Aromatic amines used may be substituted or unsubstituted amines. Preferably the amines, if they are substituted, ought not to possess any substituents in para position. Examples of suitable aromatic amines are N-methylaniline, N-ethylaniline, o-toluidine, o-chloroaniline, m-chloroaniline, o-anisidine, 2,3-xylidine, 3,5-xylidine, o-cyclohexylaniline, o-benzylaniline, alpha-naphthylaniline, methylmercaptoaniline or aniline. Particular preference is given to the use of aniline as aromatic amine.
In the preparation process of the invention the following composition and isomer ratios are obtained, preferably distributed as follows:
  • 74% to 85% by weight 4,4′-diaminodiphenylalkane,
  • 3% to 20% by weight, preferably 7% to 15% by weight, 2,4′-diaminodiphenyl-alkane
  • and
  • ≦1% by weight, preferably ≦0.8% by weight 2,2′-diaminodiphenylalkane.
With the process of the invention it is preferred to prepare diaminodiphenyl-methane with the following isomer composition:
  • 74% to 85% by weight 4,4′-diaminodiphenylmethane,
  • 3% to 20% by weight, preferably 7% to 15% by weight, 2,4′-diaminodiphenyl-methane
  • and
  • ≦1% by weight, preferably ≦0.8% by weight 2,2′-diaminodiphenylmethane.
The fraction of polynuclear compounds in the isomer mixture of the diaminodiphenylalkane, more particularly of diaminodiphenylmethane, is 10% by weight, preferably <10% by weight. Polynuclear compounds for the purposes of the invention are those molecules having more than two aromatic nuclei, more particularly phenyl rings.
The N-methyl compound impurities in the isomer mixture of the diaminodiphenylalkane, more particularly diaminodiphenylmethane, are ≦1.0% by weight, preferably ≦0.5% by weight and more preferably ≦0.3% by weight.
This isomer distribution is particularly suitable for further processing via diaminodicyclohexylmethane to the corresponding diisocyanatodicyclohexylmethane compound. The isomer ratio obtained in the process of the invention also determines the subsequent isomer ratio in the diisocyanate compound.
With the process of the invention the required isomer ratio is obtained at the diaminodiphenylalkane preparation stage itself, without having to be brought about by means of additional separation processes, which are inconvenient and expensive. Moreover, such purification processes are a disadvantage in view of the fact that the substances involved are very reactive, and so possible side reactions may occur in the course of purification or distillation.
A further advantage of the process of the invention is that the fraction of unwanted by-products, especially N-methyl compounds, is very low. On further processing to the diisocyanate, N-methyl compounds lead to unwanted monoisocyanates and hence to a deterioration in the quality of the product.
The prior-art processes operating with acidic ion exchangers as catalysts lead to significantly higher isomer fractions of 4,4′-diaminodiphenylalkane. For instance, in the examples of publication EP 0 043 933, the corresponding amounts are 94% by weight, 92% by weight and 91% by weight. These isomer contents, however, are too high, since the further processing to form the aliphatic diisocyanate compound is accompanied by crystallization, which is unwanted.
The diaminodiphenylalkanes obtained according to EP 0 043 933 must therefore be brought by means of additional process steps, such as distillation, to the desired isomer ratio of 74% to 85% by weight 4,4′-diaminodiphenylalkane, 3% to 20% by weight 2,4′-diaminodiphenylalkane and ≦1.0% by weight 2,2′-diaminodiphenylalkane. Moreover, the level of polynuclear compounds, at ≦10% by weight, is favourably low in accordance with the invention.
A further advantage of the process of the invention lies in its environmental and economic performance. The catalytic reaction is performed preferably at a reaction temperature in the range from 80 to 140° C., more preferably 80 to 130° C. and very preferably 80 to 120° C. The required reaction time for the catalytic reaction is preferably 30 minutes to 5 hours, more preferably 0.75 hour to 4.5 hours and very preferably 0.75 to 3.0 hours.
These reaction times are considerably lower in comparison to EP 0 043 933. From the examples of the publication it is apparent that the reaction times there are up to 20 hours and are therefore around twenty times higher than in the case of the process of the present invention. The reaction temperature is similarly high, and this implies an approximately twentyfold higher energy consumption for the implementation of the reaction.
The process of the invention therefore possesses the advantage that it can be carried out less expensively and more economically and also, by virtue of the shorter reaction time, affords a greater conversion per unit time.
The yields in the process of the invention as well are higher than in the prior art. Thus the yields according to EP 0 043 933 in the examples are situated in the range from 60% to 78% by weight. In comparison to this, in the case of the process of the present invention, overall yields of 80% to 95% by weight are obtained, as defined in the examples.
The starting substances used are preferably aromatic amine and aldehyde in a molar ratio of 5:1 to 15:1, preferably 7:1 to 12:1 and very preferably 10:1. It is preferred to use the amine in excess, since this increases the selectivity. Excess amine can be removed by distillation after the conclusion of the reaction.
Catalysts used are mesoporous, acidic ion exchangers based on divinylbenzene/styrene copolymers. The catalyst can be used in the dry or moist state. Acidic groups used are preferably sulphonic acid groups. The catalyst is prepared, for example, by copolymerization of styrene with divinylbenzene and sulphonation using sulphuric acid/oleum.
The process of the invention can be carried out, in a preferred way, continuously, batchwise or semi-batchwise.
In a preferred embodiment the reaction is implemented in a stirred tank, a stirred-tank cascade, a flow tube, one or more fixed-bed reactors, or a column. The catalytic reaction is carried out over a heterogeneous catalyst.
For the implementation of the process of the invention the starting substances, aromatic amine and aldehyde, are mixed continuously or discontinuously. The catalytic reaction then takes place at temperatures in the range from 80 to 140° C.
Thereafter the isomer mixture of the diaminodiphenylalkanes is isolated by customary separation methods.
The examples below illustrate the invention.
EXAMPLES Examples 1 to 4
232.5 g of aniline and 60 g of the moist ion-exchange resin Amberlyst 36Wet, containing sulphone groups, were brought together under an N2 atmosphere in a stirred container and were heated to 80 to 120° C. with stirring. The ion-exchange resin used has a concentration of acidic centres, according to the manufacturer's product datasheet, of at least 5.4 eq/kg and an average pore diameter of 240 Å (corresponding to 24 nm). At theses temperatures 20 g of formaldehyde solution (37% by weight formaldehyde in water), corresponding to an aniline/formalin molar ratio of 10:1, were metered in over the course of 60 minutes.
The composition of the reaction product (analysis by gas chromatography following removal of the aniline present in excess) is as follows:
N-Methyl Polynuclear
2,2′ isomer 2,4′ isomer 4,4′ isomer compound compound
No. Temp. ° C. wt. % wt. % wt. % wt. % wt. %
1 80 0.36 10.91 80.00 0.03 8.71
2 100 0.38 12.60 77.57 0.13 9.36
3 110 0.53 13.84 75.93 0.14 9.57
4 120 0.75 15.22 74.22 0.15 9.85
Example 5
232.5 g of aniline and 60 g of the moist ion-exchange resin Amberlyst 15Wet, containing sulphone groups, were brought together under an N2 atmosphere in a stirred container and were heated to 100° C. with stirring. The ion-exchange resin used has a concentration of acidic centres, according to the manufacturer's product datasheet, of at least 4.7 eq/kg and an average pore diameter of 300 Å (corresponding to 30 nm). At this temperature 20 g of formaldehyde solution (37% by weight formaldehyde in water), corresponding to an aniline/formalin molar ratio of 10:1, were metered in over the course of 60 minutes.
The composition of the reaction product (analysis by gas chromatography following removal of the aniline present in excess) is as follows:
N-Methyl Polynuclear
2,2′ isomer 2,4′ isomer 4,4′ isomer compound compound
No. Temp. ° C. wt. % wt. % wt. % wt. % wt. %
5 100 0.14 12.82 79.32 0.37 7.28
These examples show that the required isomer ratio can be generated without further purification or distillation steps. The reaction times needed for complete formaldehyde conversion were 240 minutes for Example 1, 140 minutes for Example 2 and 60 minutes for Examples 3, 4 and 5. The selectivities (yields) are high and amount to 91.3% by weight in Example 1, 90.5% by weight in Example 2, 90.3% by weight in Example 3, 90% by weight in Example 4 and 90.3% by weight in Example 5.
The tables show that the required isomer ratio can be generated without further purification or distillation steps. The selectivity (S) of the reaction is calculated from the ratio between the amount of substance of the desired product (P) formed (in this case the sum of the 2,2′, 2,4′ and 4,4′ isomers of MDA) and the amount of substance of the key component (K) reacted (in this case formaldehyde), taking into account the stoichiometric numbers (v). For batch operation, therefore:
S P = n 0 n K 0 - n K · v K v P · 100
After the stated number of minutes the full conversion of the formaldehyde employed was achieved. Accordingly the selectivity of the reaction is identical with the yield.

Claims (18)

1. A process for preparing a bis(aminophenyl)alkane, comprising reacting an aromatic amine, which may be substituted or unsubstituted, with a C1-C3 aldehyde in the presence of a heterogeneous catalyst, the catalyst being a mesoporous acidic ion exchanger based on a divinylbenzene/styrene copolymer, and the catalyst comprising an acidic center, measured in accordance with DIN 54 403, in a concentration of 4 to 6 eq/kg, and the average pore diameter of the catalyst particles, measured in accordance with ASTM D 4222, being 10 to 32 nm, and the polynuclear compound content of the reaction mixture formed being 10% by weight.
2. The process according to claim 1, wherein the aldehyde is formaldehyde.
3. The process according to claim 1, wherein the amine is aniline.
4. The process according to claim 1, wherein the bis(aminophenyl)alkane obtained is diaminodiphenylmethane.
5. The process according to claim 1, wherein the isomer ratio of the bis(aminophenyl)alkane obtained is distributed as follows:
74% to 85% by weight 4,4′-bis(aminophenyl)alkane 3% to 20% by weight 2,4′-bis(aminophenyl)alkane ≦1.0% by weight 2,2′-bis(aminophenyl)alkane.
6. The process according to claim 5, wherein the isomer ratio of the bis(aminophenyl)alkane obtained is distributed as follows:
74% to 85% by weight 4,4′-bis(aminophenyl)alkane 3% to 20% by weight 2,4′-bis(aminophenyl)alkane ≦1.0% by weight 2,2′-bis(aminophenyl)alkane.
7. The process according to claim 1, wherein the N-methyl compound content is ≦1% by weight.
8. The process according to claim 1, wherein the polynuclear compound content is <10% by weight.
9. The process according to claim 1, wherein the reaction temperature of the catalytic reaction is situated in the range from 80 to 140° C.
10. The process according to claim 1, wherein the reaction time for the catalytic reaction is 30 min to 5 hours.
11. The process according to claim 1, wherein the molar ratio of amine to aldehyde is 5:1 to 15:1.
12. The process according to claim 1, wherein the catalyst is in dry or moist form.
13. The process according to claim 1, wherein the process is carried out continuously, batchwise or semi-batchwise.
14. The process according to claim 1, wherein the reaction is carried out in a stirred tank, a stirred-tank cascade, a flow tube, a fixed-bed reactor or in a column.
15. The process according to claim 1, wherein the acidic center comprises a sulfonic acid group.
16. The process according to claim 1, wherein the concentration of the acidic centers of the ion exchanger is 4.4 to 5.7 eq/kg and very preferably 4.7 to 5.6 eq/kg, measured in accordance with DIN 54 403.
17. The process according to claim 1, wherein the pore diameter of the ion exchangers, measured in accordance with ASTM D 4222, is 15 up to and including 30 nm.
18. The process according to claim 1, wherein the reaction temperature of the catalytic reaction is in the range from 80 to 130° C.
US12/867,168 2008-04-30 2009-03-26 Method for producing diaminodiphenyl alkanes Active 2029-12-24 US8389770B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102008001492 2008-04-30
DE102008001492.3 2008-04-30
DE102008001492A DE102008001492A1 (en) 2008-04-30 2008-04-30 Process for the preparation of diaminodiphenylalkanes
PCT/EP2009/053583 WO2009132906A2 (en) 2008-04-30 2009-03-26 Method for producing diaminodiphenyl alkanes

Publications (2)

Publication Number Publication Date
US20100312014A1 US20100312014A1 (en) 2010-12-09
US8389770B2 true US8389770B2 (en) 2013-03-05

Family

ID=41055392

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/867,168 Active 2029-12-24 US8389770B2 (en) 2008-04-30 2009-03-26 Method for producing diaminodiphenyl alkanes

Country Status (6)

Country Link
US (1) US8389770B2 (en)
EP (1) EP2268602B1 (en)
JP (1) JP5936352B2 (en)
CN (1) CN101570489B (en)
DE (1) DE102008001492A1 (en)
WO (1) WO2009132906A2 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008001469A1 (en) * 2008-04-30 2009-11-05 Evonik Degussa Gmbh Process for the preparation of diaminodiphenylalkanes
CN102399155B (en) * 2011-12-29 2014-03-26 河南省华鼎高分子合成树脂有限公司 Method for preparing 4,4-methylenedianiline

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0043933A1 (en) 1980-07-12 1982-01-20 BASF Aktiengesellschaft Process for the preparation of polyamine mixtures with a big portion of 4,4'-diamino-diphenyl methane
US4554378A (en) 1983-02-22 1985-11-19 The Dow Chemical Company Process for preparing polyamines with ion exchange resin catalysts

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB991157A (en) 1962-12-10 1965-05-05 Jefferson Chem Co Inc Polyamine preparation
BE667830A (en) 1964-08-24 1965-12-01
US4071558A (en) 1967-09-28 1978-01-31 Texaco Development Corporation Aromatic polyamines and their preparation
US4039581A (en) 1975-06-27 1977-08-02 The Upjohn Company Process for the preparation of di(amino phenyl)methanes
US4039580A (en) 1975-07-24 1977-08-02 The Upjohn Company Process for preparing di(aminophenyl)methanes
DE2736862A1 (en) * 1977-08-16 1979-03-01 Bayer Ag PROCESS FOR PRODUCING POLYAMINES OF THE DIPHENYLMETHANE SERIES
US4294981A (en) 1979-04-02 1981-10-13 The Upjohn Company 13,14-Didehydro-11-deoxy-9-deoxy-9-methylene-19-oxo-PGF1 compounds
DE3142529A1 (en) * 1981-10-27 1983-05-05 Lentia GmbH Chem. u. pharm. Erzeugnisse - Industriebedarf, 8000 München METHOD FOR PRODUCING DIAMINES OF THE DIPHENYLMETHANE SERIES
WO1987002979A1 (en) * 1985-11-12 1987-05-21 The Dow Chemical Company A process for continuously preparing aromatic polyamines with ion exchange resin catalysts
JP4357393B2 (en) * 2004-09-16 2009-11-04 三井化学株式会社 Method for producing aromatic polyamine
DE102008001469A1 (en) * 2008-04-30 2009-11-05 Evonik Degussa Gmbh Process for the preparation of diaminodiphenylalkanes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0043933A1 (en) 1980-07-12 1982-01-20 BASF Aktiengesellschaft Process for the preparation of polyamine mixtures with a big portion of 4,4'-diamino-diphenyl methane
US4554378A (en) 1983-02-22 1985-11-19 The Dow Chemical Company Process for preparing polyamines with ion exchange resin catalysts

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Siril et al., "New polystyrene sulfonic acid resin catalysts with enhanced acidic and catalytic properties", Journal of Molecular Catalysys A: Chemical, vol. 279, No. 1, pp. 63-68, XP022376501, ISSN: 1381-1169, (Oct. 7, 2007).
U.S. Appl. No. 12/866,833, filed Aug. 9, 2010, Kreczinski, et al.
U.S. Appl. No. 12/922,280, filed Sep. 13, 2010, Grund, et al.

Also Published As

Publication number Publication date
US20100312014A1 (en) 2010-12-09
WO2009132906A3 (en) 2009-12-30
EP2268602A2 (en) 2011-01-05
JP2011518851A (en) 2011-06-30
WO2009132906A2 (en) 2009-11-05
CN101570489B (en) 2016-05-18
EP2268602B1 (en) 2018-10-31
DE102008001492A1 (en) 2009-11-05
JP5936352B2 (en) 2016-06-22
CN101570489A (en) 2009-11-04

Similar Documents

Publication Publication Date Title
US6649798B2 (en) Method for production of diaminodiphenylmethanes
US4092343A (en) Polymethylene polyphenyl polyisocyanate
US8536370B2 (en) Low chlorine, multi-staged method for producing cycloaliphatic disocyanates
US8822726B2 (en) Method for producing diaminodiphenyl alkanes
KR101613332B1 (en) Process for production of methylene-bridged polyphenyl polyamines
US8389770B2 (en) Method for producing diaminodiphenyl alkanes
EP1268395B1 (en) Process for the preparation of mixtures of methylenedianiline and its higher homologous products
KR100969745B1 (en) Process for the production of diaminodiphenylmethane and its higher homologues
EP2268713B1 (en) Process for making polyaminopolyphenyl methanes using a mixed solid acid catalyst system
JPS5883658A (en) Manufacture of diamines of diphenylmethane series

Legal Events

Date Code Title Description
AS Assignment

Owner name: EVONIK DEGUSSA GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GRUND, GERDA;KRECZINSKI, MANFRED;REEL/FRAME:024840/0148

Effective date: 20100622

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: EVONIK OPERATIONS GMBH, GERMANY

Free format text: CHANGE OF NAME;ASSIGNOR:EVONIK DEGUSSA GMBH;REEL/FRAME:051765/0166

Effective date: 20191002

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8